Semiconductors

ABSTRACT

The present invention relates to polymers comprising a repeating unit of the formula—[Ar3]c—[Ar2]b—[Ar1]a—Y(R1)n1 (R2)n2—[Ar1′]a—[Ar2′]b′—[Ar3′]c′— (I), wherein γ is a bivalent heterocyclic group, or ring system, which may optionally be substituted, Ar1, Ar1′Ar2, Ar2′, Ar3 and Ar3′ are independently of each other a C6-C24 arylen group, which can optionally be substituted, or a C2-C30 heteroarylen group, which can optionally be, Formula (1), substituted; at least one of R1 and R2 is a group of formula (II); and their use as organic semiconductor in organic devices, especially in organic photovoltaics and photodiodes, or in a device containing a diode and/or an organic field effect transistor. The polymers according to the invention can have excellent solubility in organic solvents and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the polymers according to the invention are used in organic field effect transistors, organic photovoltaics and photodiodes.

The present invention relates to polymers comprising a repeating unit ofthe formula (I) and their use as organic semiconductor in organicdevices, especially in organic photovoltaics and photodiodes, or in adevice containing a diode and/or an organic field effect transistor. Thepolymers according to the invention can have excellent solubility inorganic solvents and excellent film-forming properties. In addition,high efficiency of energy conversion, excellent field-effect mobility,good on/off current ratios and/or excellent stability can be observed,when the polymers according to the invention are used in organic fieldeffect transistors, organic photovoltaics and photodiodes.

Diketopyrrolopyrrole (DPP) based polymers and copolymers are described,for example, in U.S. Pat. No. 6,451,459, WO05/049695, WO08/000664,EP2075274A1, WO2010/049321, WO2010/049323, WO2010/108873, WO2010/115767,WO2010/136352, WO2011/144566 and WO2011/144566.

Isoindigo based polymers and copolymers are described, for example, inWO2009/053291, PCT/IB2015/055118, US2014/0011973 and PCT/EP2016/050801.Naphthaleneimide based polymers and copolymers are described, forexample, in WO2009098253.

Peryleneimide based polymers and copolymers are described, for example,in WO2009098250, WO2009098252, WO2009098253 and WO2009098254.

B. Fu et al., Adv. Funct. Mater. 2014, 24, 3734-3744 reports that theincorporation of side chains in which the branch position is remote fromthe polymer backbone combines the benefit of branched side chains inimproving solubility with linear chains in promoting efficient π-πinter-molecular interactions. This provides a polymer with enhancedsolution processability, a higher degree of polymerization, close π-πintermolecular stacking, and, in turn, superior macroscale chargecarrier transport.

U.S. Pat. No. 5,750,723 relates to polymerisable diketopyrrolopyrroles

wherein A and B are independently of each other a group of formula

R¹ is a reactive group capable of polymerization(—(CH₂)_(m)—CH═CH—(CH₂)_(n)—CH₃ (II), or —(Y)_(p)—X—(Z)_(r)-Q (III)),and R² is C₁-C₆alkyl, or R¹, m and n independently of one another are aninteger between zero and 12, with the proviso that the sum m+n is atleast 4, such as, for example,

US2005/0255391 relates to the use of polymerisable diketopyrrolopyrrolesin colour filters.

Among others diketopyrrolopyrroles of the general formula

are disclosed, wherein R₁ and R₂ are independently of each other a groupof the formula—X₂-X₃(II), wherein X₂ is C₁-C₁₈alkylene and X3 is —NH₂,—OH, —CH═CH₂, —C(CH₃)═CH₂, —CO—CH═CH₂, —CO—C(CH₃)═CH₂, —CO—CH═CH₂ or—CO—C(CH₃)═CH₂, such as, for example,

Reference is also made to US2009140220.

It was an aim of the present invention to reduce or overcome thedisadvantages in organic semiconductor (OSC) layers of prior art, toprovide improved electronic devices, to provide improved OSC materialsand components to be used in such devices, and to provide methods fortheir manufacture. The device should exhibit improved stability, highfilm uniformity and high integrity of the OSC layer, the materialsshould have a high charge mobility and good processibility fromsolution, and the method should enable easy and time- and cost-effectivedevice production especially at large scale. Other aims of the presentinvention are immediately evident to the expert from the followingdetailed description.

Accordingly, it is the object of the present invention to providepolymers, which show high efficiency of energy conversion, excellentfield-effect mobility, good on/off current ratios and/or excellentstability, when used in organic field effect transistors, organicphotovoltaics (solar cells) and photodiodes. Another object of theinvention is to provide semiconducting polymers, which can becrosslinked.

Said object has been solved by polymers, comprising a repeating unit offormula—[Ar³]_(c)—[Ar²]_(b)—[Ar¹]_(a)—Y(R¹)_(n1)(R²)_(n2)—[Ar^(1′)]_(a′),—[Ar^(2′)]_(b′), —[Ar^(3′)]_(c′)—  (I),wherein

a is 0, 1, 2, or 3, a′ is 0, 1, 2, or 3; b is 0, 1, 2, or 3; b′ is 0, 1,2, or 3; c is 0, 1, 2, or 3; c′ is 0, 1, 2, or 3;

n1 is 1, or 2, n2 is 1, or 2,

Y is a bivalent heterocyclic group, or ring system, which may optionallybe substituted,

Ar¹, Ar^(1′), Ar², Ar^(2′), Ar³ and Ar^(3′) are independently of eachother a C₆-C₂₄arylen group, which can optionally be substituted, or aC₂-C₂₀heteroarylen group, which can optionally be substituted;

R¹ and R² in each occurrence are independently of each other hydrogen,C₅-C₁₂cycloalkyl, COR³⁸, C₁-C₅₀alkyl, C₃-C₅₀alkenyl, or C₃-C₅₀alkynyl,which can optionally be substituted one or more times with C₁-C₁₂alkoxy,halogen, C₅-C₈cycloalkyl, cyano, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or asilyl group; and/or can optionally be further interrupted by one or more—O—, —S—, —NR³⁹—, —CONR³⁹—, —NR³⁹CO—, —COO—, —CO—, or —OCO—, or a groupof formula

i is an integer from 1 to 18,

R⁷⁰, R⁷¹ and R⁷² are independently of each other hydrogen, C₁-C₅₀alkyl,C₅-C₁₂cycloalkyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, C₂-C₅₀alkenyl orC₂-C₅₀alkynyl which can optionally be substituted one or more times withC₁-C₁₂alkoxy, halogen (especially F), C₅-C₈cycloalkyl, cyano,C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or a silyl group; and/or can optionally befurther interrupted by one or more —O—, —S—, —NR³⁹—, —CONR³⁹—, —NR³⁹CO—,—COO—, —CO—, or —OCO—; with the proviso that at least one of thesubstituents R⁷⁰, R⁷¹ and R⁷² is different from hydrogen;

R³⁸ is C₁-C₅₀alkyl, C₂-C₅₀alkenyl, C₂-C₅₀alkynyl or C₁-C₅₀alkoxy, whichcan optionally be substituted one or more times with C₁-C₁₂alkoxy,halogen, C₅-C₈cycloalkyl, cyano, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or asilyl group; and/or can optionally be further interrupted by one or more—O—, —S—, —NR³⁹—, —CONR³⁹—, —NR³⁹CO—, —COO—, —CO—, or —OCO—, and R³⁹ ishydrogen, C₁-C₂₅alkyl, C₁-C₁₈haloalkyl, C₇-C₂₅arylalkyl, orC₁-C₁₈alkanoyl, with the proviso that at least one of R¹ and R² is agroup of formula (II).

FIG. 1 shows representative transfer characteristics of an FETfabricated from compound P1 with VGS=10 V to −30 V at 0.5V step sizewith VDS=−30V. Drain current (black solid curve), Gate current (dottedgrey curve), Square root of drain current (grey solid curve), and fittedslope of square root (dashed black curve).

The polymers of the invention can be used as the semiconductor layer insemiconductor devices. Accordingly, the present invention also relatesto semiconductor devices, or an organic semiconductor material, layer orcomponent, comprising a polymer of the present invention. Thesemiconductor device is especially an organic photovoltaic (PV) device(solar cell), a photodiode, or an organic field effect transistor. Thesemiconducting polymers of the present invention show a good mobilityand in addition a good solubility, which makes them suitable for deviceswhere the semiconductor is applied e.g. by printing processes.

Examples of the bivalent heterocyclic group, or ring system, Y, areshown below.

Besides the substituents R¹ and R² Y can be substituted with one to foursubstituents independently selected from the group consisting ofC₁-C₂₅alkyl, C₂-C₂₅alkenyl, C₂-C₂₅alkynyl, C₅-C₈cycloalkyl, C₆-C₁₄aryl,C₂-C₂₀heteroaryl, —OR¹¹⁰, —OC(O)—R¹¹⁰, —C(O)—OR¹¹⁰, —C(O)—R¹¹⁰,—NR¹¹⁰R¹¹¹, —NR¹¹⁰—C(O)R¹¹¹, —C(O)—NR¹¹⁰R¹¹¹, —N[C(O)R¹¹⁰][C(O)R¹¹¹],—SR¹¹⁰, halogen, CN, —SiR¹¹²R¹¹³R¹¹⁴ and —NO₂, wherein R¹¹⁰ and R¹¹¹ areindependently selected from the group consisting of H, C₁-C₂₅alkenyl,C₃-C₂₅alkynyl, C₃-C₂₅C₅-C₈cycloalkyl, C₆₋₁₄aryl and C₂-C₂₀heteroaryl,R¹¹², R¹¹³ and R¹¹⁴ are independently from each other selected from thegroup consisting of H, C₁-C₂₅alkenyl, C₂-C₂₅alkynyl, C₅-C₈cycloalkyl,phenyl and O—Si(CH₃)₃. More preferred additional substituents of Y areF, C₁-C₂₅alkyl and —OR¹¹⁰, wherein R¹¹⁰ is C₁-C₂₅alkyl. Most preferred Ybears no additional substituents with the exception of R¹ and R².

The group of formula Y(R¹)_(n1)(R²)_(n2) is preferably a group offormula

which may optionally be substituted, wherein R¹ and R² are definedabove, or below and R^(1′) and R^(2′) have the meaning of R¹, with theproviso that in case Y(R¹)_(n1)(R²)_(n2) is a group of formula

a and a′ in formula (I) are not 0. That is, the group of formula (IIIa)comprises at

least one group Ar¹ and Ar^(1′).

The group of formula Y(R¹)_(n1)(R²)_(n2) is more preferably a group offormula (IIIa), (IIIb), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), or(IIIi), even more preferably a group of formula (IIIa), (IIIb), (IIId),(IIIe), (IIIh), or (IIIi), most preferably a group of formula (IIIa),(IIIb), or (IIId).

Examples of C₆-C₁₄arylen, C₆-C₂₄arylen groups and C₂-C₂₀heteroarylengroups, Ar¹, Ar^(1′) Ar², Ar^(2′), Ar³ and Ar^(3′), which can optionallybe substituted, are shown below.

C₆-C₁₄arylen, C₆-C₂₄arylen groups and C₂-C₂₀heteroarylen groups can besubstituted with one to ten substituents independently selected from thegroup consisting of C₁-C₂₅alkyl, C₂-C₂₅alkenyl, C₂-C₂₅alkynyl,C₅-C₈cycloalkyl, C₆-C₁₄aryl, C₂-C₂₀heteroaryl, OR¹¹⁰, OC(O)—R¹¹⁰,C(O)—OR¹¹⁰, C(O)—R¹¹⁰, NR¹¹⁰R¹¹¹, NR¹¹⁰—C(O)R¹¹¹, C(O)—NR¹¹⁰R¹¹¹,N[C(O)R¹¹⁰][C(O)R¹¹¹], SR¹¹⁰, halogen, CN, SiR¹¹²R¹¹³R¹¹⁴ and NO₂,wherein R¹¹⁰ and R¹¹¹ are independently selected from the groupconsisting of H, C₁-C₂₅alkenyl, C₂-C₂₅alkenyl, C₂-C₂₅alkynyl,C₅-C₈cycloalkyl, C₆-C₁₄aryl and C₂-C₂₀heteroaryl, R112, R¹¹³ and R¹¹⁴are independently from each other selected from the group consisting ofH, C₁-C₂₅alkyl, C₂-C₂₅alkenyl, C₂-C₂₅alkynyl, C₅-C₈cycloalkyl, phenyland O—Si(CH₃)₃.

Preferably C₆-C₁₄arylen, C₆-C₂₄arylen groups and C₂-C₂₀heteroarylengroups can be substituted with one to ten substituents independentlyselected from the group consisting of C₁-C₂₅alkyl, OR¹¹⁰, halogen andSiR¹¹²R¹¹³R¹¹⁴, wherein R¹¹⁰ is selected from the group consisting of Hand C₁-C₂₅alkyl, and R¹¹², R¹¹³ and R¹¹⁴ are independently from eachother selected from the group consisting of H, C₁-C₂₅alkyl, phenyl andO—Si(CH₃)₃.

More preferably C₆-C₁₄arylen, C₆-C₂₄arylen groups, or C₂-C₂₀heteroarylengroups can be substituted with one to ten substituents independentlyselected from the group consisting of C₁-C₂₅alkyl, OR¹¹⁰ and halogen,wherein R¹¹⁰ is selected from the group consisting of H and C₁-C₂₅alkyl.

Most preferably C₆-C₁₄arylen, C₆-C₂₄arylen groups, or C₂-C₂₀heteroarylengroups are not substituted.

Ar¹ and Ar^(1′) are independently of each other a group of formula

wherein R³ and R^(3′) are independently of each other hydrogen, halogen,halogenated C₁-C₂₅alkyl, especially CF₃, cyano, C₁-C₂₅alkyl, especiallyC₃-C₂₅alkyl, which may optionally be interrupted by one or more oxygenor sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy; R⁴, R^(4′), R⁵,R^(5′), R⁶ and R^(6′) are independently of each other hydrogen, halogen,halogenated C₁-C₂₅alkyl, especially CF₃, cyano, C₁-C₂₅alkyl, especiallyC₃-C₂₅alkyl, which may optionally be interrupted by one or more oxygenor sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy; R⁷, R^(7′), R⁹ andR^(9′) are independently of each other hydrogen, C₁-C₂₅alkyl, especiallyC₃-C₂₅alkyl, which may optionally be interrupted by one, or more oxygen,or sulphur atoms; or C₇-C₂₅arylalkyl,

R⁸ and R^(8′) are independently of each other hydrogen, C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₂₅alkyl, or C₁-C₂₅alkoxy; orC₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally be interruptedby one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl, R¹¹ andR^(11′) are independently of each other C₁-C₂₅alkyl group, especially aC₁-C₈alkyl group, C₇-C₂₅arylalkyl, or a phenyl group, which can besubstituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy;

R¹² and R^(12′) are independently of each other hydrogen, halogen,cyano, C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally beinterrupted by one, or more oxygen, or sulphur atoms, C₁-C₂₅alkoxy,C₇-C₂₅arylalkyl, or

wherein

R¹³ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group;

R^(103′) is C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally beinterrupted by one, or more oxygen, or sulphur atoms, and

R¹¹⁴ and R^(114′) are independently of each other hydrogen, cyano,COOR^(103′), a C₁-C₂₅alkyl group, or C₆-C₁₄aryl or C₂-C₂₀heteroaryl.

Ar¹ and Ar^(1′) are preferably a group of formula XIa-1, XIa-2, XIa-4,XIb, XId, XIi, XIm, or XIz-1, more preferably a group of formula XIa-1,XIa-2, XIa-4, XId, or XIi, even more preferably a group of formulaXIa-1, XIa-2, XIa-4, or XId, most preferably a group of formula XIa-1,or XIa-4.

Ar², Ar^(2′), Ar³ and Ar^(3′) have independently of each other themeaning of Ar¹, wherein Ar¹ is defined above, or below, or areindependently of each other

R¹⁰³ is C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally beinterrupted by one, or more oxygen, or sulphur atoms;

R¹⁰⁴ and R^(104′) are independently of each other hydrogen, cyano,COOR¹⁰³, a C₁-C₂₅alkyl group, or C₆-C₁₄aryl or C₂-C₂₀heteroaryl,

R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are independently of each otherhydrogen, halogen, cyano, C₁-C₂₅alkyl, which may optionally beinterrupted by one or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, orC₁-C₂₅alkoxy,

R¹⁰⁷ is hydrogen, C₇-C₂₅arylalkyl, C₆-C₂₀aryl; C₆-C₂₀aryl which issubstituted by C₁-C₂₅alkyl, or C₁-C₂₅alkoxy; C₁-C₁₈perfluoroalkyl;C₁-C₂₅alkyl; especially C₃-C₂₅alkyl, which may be interrupted by —O—, or—S—; or —COOR¹⁰³;

R¹⁰⁸ and R¹⁰⁹ are independently of each other hydrogen, C₁-C₂₅alkyl,especially C₃-C₂₅alkyl, which may optionally be interrupted by one, ormore oxygen, or sulphur atoms; or C₇-C₂₅arylalkyl,

R¹¹⁵ and R^(115′) are independently of each other hydrogen, halogen,cyano, C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally beinterrupted by one, or more oxygen, or sulphur atoms, C₁-C₂₅alkoxy,C₇-C₂₅arylalkyl, or

wherein R¹¹⁶ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group.

Ar², Ar^(2′), Ar³ and Ar^(3′) are preferably a group of formula XIa-1,XIa-2, XIa-4, XIb, XId, XIi, XIm, XIx-1, XIx-2, XIx-3, XIx-5, XIz-1,XIIIa, XIIIb-1, XIIIb-2, XIIIe, XIIIg-2, XIIIi-1, or XIIIj; morepreferably a group of formula XIa-1, XIa-2, XIa-4, XId, XIi, XIx-1,XIx-2, XIIIa, XIIIg-2, or XIIIi-1; even more preferably a group offormula XIa-1, XIa-2, XIa-4, XId, or XIIi-1, most preferably a group offormula XIa-1, XIa-4, or XIIIi-1.

a is 0, 1, 2, or 3, a′ is 0, 1, 2, or 3; bis 0, 1, 2, or 3; b′ is 0, 1,2, or 3; cis 0, 1, 2, or 3; c′ is 0, 1, 2, or 3; preferably a is 0, 1,or 2; a′ is 0, 1, or 2; b is 0, 1, or 2; b′ is 0, 1, or 2; c is 0, 1, or2; c′ is 0, 1, or 2; more preferably a is 0, 1, or 2; a′ is 0, 1 or 2; bis 0, or 1; b′ is 0, or 1; c is 0, or 1; c′ is 0, or 1; even morepreferably a is 0, 1, or 2, a′ is 0, 1 or 2; b is 0; b′ is 0; c is 0; c′is 0; most preferably a is 0, or 1; a′ is 0, or 1; b is 0; b′ is 0; c is0; c′ is 0.

The repeating unit of formula (I) is preferably a repeating unit offormula

more preferably a repeating unit of formula (Ia), (Ic), (Ie), (If),(Ij), or (Ik), most preferably a repeating unit of formula (Ia), (Ic),(Ie), or (If), wherein

R³ and R^(3′) are independently of each other hydrogen, halogen,especially fluorine, C₁-C₂₅alkyl, or C₁-C₂₅alkoxy, and

R¹, R², R^(1′) and R^(2′) are defined above, or below.

In a preferred embodiment the present invention is directed to polymers,comprising a repeating unit -[A]-[COM]_(n3)- (V), wherein A is a unit offormula (I) and COM has the meaning of —Ar²—, wherein Ar² is definedabove, or below, n3 is an integer of 1 to 4, especially 1 to 3 and COMcan be the same or, different in each occurrence.

In another preferred embodiment the present invention is directed topolymers of formula -[[A]-[COM]_(n3)]_(n)- (V′), wherein A is a unit offormula (I) and COM has the meaning of —Ar²—, wherein Ar² is definedabove, or below, n3 is an integer of 1 to 4, especially 1 to 3 and COMcan be the same or, different in each occurrence, n is 4 to 1000,especially 5 to 200, very especially 6 to 100.

COM is preferably a group of formula XIa-1, XIa-2, XIa-4, XIb, XId, XIi,XIm, XIx-1, XIx-2, XIx-3, XIx-5, XIz-1, XIIIa, XIIIb-1, XIIIb-2, XIIIe,XIIIg-2, XIIII-1, or XIIIj; more preferably a group of formula XIa-1,XIa-2, XIa-4, XId, XIi, XIx-1, XIx-2, XII Ia, XIIIg-2, or XIIIi-1; evenmore preferably a group of formula XIa-1, XIa-2, XIa-4, XId, or XIIIi-1,most preferably a group of formula XIa-1, XIa-4, or XIIIi-1.

In said embodiment polymers are preferred, comprising repeating units-[A]-[COM]_(n3)- of formula

wherein

R³ and R^(3′) are independently of each other hydrogen, fluorine,C₁-C₂₅alkyl, or C₁-C₂₅alkoxy, and R¹ and R² are defined above, or below.

R³ and R^(3′) are preferably hydrogen.

The repeating unit of formula -[A]-[COM]_(n3)- is preferably areapeating unit of formula Va, Vb, Vd, Ve, Vf, Vg, Vj, Vk, Vl, Vn, Vo,or Vp, more preferably a repeating unit of formula Va, Vb, Vd, Ve, Vf,Vn, Vo, or Vp, even more preferably a repeating unit of formula Va, Vb,or Vp, most preferred a repeating unit of formula Va.

Preferably the total weight of the repeating units -[A]-[COM]_(n3)- in apolymer of the present invention is more than 5 weight percent,preferably more than 20%, more preferably more than 50%, even morepreferably more than 80%, most preferably more than 90% of the totalweight of the polymer.

Examples of the polymer according to the present invention are shownbelow:

wherein n is 4 to 1000, especially 5 to 200, very especially 6 to 100,and R¹ and R² are defined above, or below.

Polymers of formulae Va′, Vb′, Vd′, Ve′, Vf′, Vn′, Vo′ and Vp′ are morepreferred. Polymers of formulae Va′, Vb′, Vd′, Ve′, Vf and Vp′ are evenmore preferred. Polymers of formula Va′ are most preferred.

R¹, R², R^(1′) and R^(2′) are preferably independently of each otherhydrogen, COR³⁸, C₁-C₅₀alkyl, C₃-C₅₀alkenyl, or C₃-C₅₀alkynyl, which canoptionally be substituted one or more times with C₁-C₁₂alkoxy, halogen,C₅-C₈cycloalkyl, cyano, C₆-C₂₀aryl, C₂-C₂₀heteroaryl, or a silyl group;and/or can optionally be further interrupted by one or more —O—, —S—,—NR³⁹—, —CONR³⁹—, —NR³⁹CO—, —COO—, —CO—, or —OCO—, or a group of formula

A silyl group is a group of formula —SiR¹⁶¹R¹⁶²R¹⁶³, wherein R¹⁶¹, R¹⁶²and R¹⁶³ are independently of each other C₁-C₈alkyl, C₅-C₆cycloalkyl,which might optionally be substituted with C₁-C₄alkyl; halogenatedC₁-C₈alkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, —(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R166,or phenyl, R¹⁶⁴, R¹⁶⁵ and R¹⁶⁶ are independently of each otherC₁-C₈alkyl, halogenated C₁-C₈alkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹,—(O—SiR¹⁶⁹R¹⁷⁰)_(d′)—R¹⁷¹, or phenyl; R¹⁶⁹, R¹⁷⁰ and R¹⁷¹ areindependently of each other C₁-C₈alkyl, halogenated C₁-C₈alkyl,C₂-C₈alkenyl, —O—Si(CH₃)₃, or phenyl; d is an integer from 1 to 10; d′is an integer from 1 to 10.

At least one of R¹, R², R^(1′) and R^(2′) is a group of formula (II).Preferably, R¹, R², R^(1′) and R^(2′) are independently of each other agroup of formula (II).

i is an integer from 1 to 18, preferably 1 to 10, more preferably 1 to5.

R⁷⁰, R⁷¹ and R⁷² are independently of each other hydrogen, C₁-C₅₀alkyl,C₅-C₈cycloalkyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, C₂-C₅₀alkenyl orC₂-C₅₀alkynyl which can optionally be substituted one or more times withC₁-C₁₂alkoxy, fluorine, C₅-C₈cycloalkyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl,or a silyl group; and/or can optionally be further interrupted by one ormore —O—, or —S—; preferably hydrogen, C₁-C₅₀alkyl, C₂-C₅₀alkenyl orC₂-C₅₀alkynyl which can optionally be substituted one or more times withfluorine; and/or can optionally be interrupted by one or more —O—, or—S—; more preferably hydrogen, C₁-C₅₀alkyl or C₂-C₅₀alkenyl; even morepreferably hydrogen, or C₁-C₅₀alkyl; most preferably hydrogen, orC₁-C₃₆alkyl, especially hydrogen, or C₆-C₂₄alkyl.

Preferably at least two of the substituents R⁷⁰, R⁷¹ and R⁷² aredifferent from hydrogen, more preferably two of the substituents R⁷⁰,R⁷¹ and R⁷² are different from hydrogen.

In case of R⁷⁰, R⁷¹ and R⁷² alkyl, alkenyl, or alkynyl can be linear orbranched and are preferably linear.

R¹, R², R^(1′) and R^(2′) are preferably independently of each other agroup of formula (II), wherein i is an integer from 1 to 10; R⁷⁰, R⁷¹and R⁷² are independently of each other hydrogen or C₁-C₅₀alkyl; withthe proviso that at least one of the substituents R⁷⁰, R⁷¹ and R⁷² isdifferent from hydrogen.

R₁, R₂, R^(1′) and R^(2′) are most preferred independently of each othera group of formula (II), wherein i is an integer from 1 to 5; and R⁷⁰,R⁷¹ and R⁷² are independently of each other hydrogen or C₁-C₃₆alkyl;with the proviso that two of the substituents R⁷⁰, R⁷¹ and R⁷² aredifferent from hydrogen.

In a preferred embodiment the present invention is directed to polymers,comprising a repeating unit of formula—[Ar³]_(c)—[Ar²]_(b)—[Ar¹]_(a)—Y(R¹)_(n1)(R²)_(n2)—[Ar^(1′)]_(a′)—[Ar^(2′)]_(b′)—[Ar^(3′)]_(c′)—  (I),wherein

a is 0, 1, or 2; a′ is 0, 1, or 2; b is 0, 1, or 2; b′ is 0, 1, or 2; cis 0, 1, or 2; c′ is 0, 1, or 2; more preferably a is 0, 1, or 2; a′ is0, 1 or 2; b is 0, or 1; b′ is 0, or 1; c is 0, or 1; c′ is 0, or 1;even more preferably a is 0, 1, or 2, a′ is 0, 1 or 2; b is 0; b′ is 0;c is 0; c′ is 0; most preferably a is 0, or 1; a′ is 0, or 1; b is 0; b′is 0; c is 0; c′ is 0;

Y(R¹)_(n1)(R²)_(n)2 is a group of formula (IIIa), (IIIb), (IIIc),(IIId), (IIIe), (IIIf), (IIIg), (IIIh), or (IIIi), Ar¹ and Ar^(1′) areindependently of each other a group of formula XIa-1, XIa-2, XIa-4, XIb,XId, XIi, XIm, or XIz-1,

Ar², Ar^(2′), Ar³ and Ar^(3′) are independently of each other a group offormula XIa-1, XIa-2, XIa-4, XIb, XId, XIi, XIm, XIx-1, XIx-2, XIx-3,XIx-5, XIz-1, XIIIa, XIIIb-1, XIIIb-2, XIIIe, XIIIi-1, or XIIIj,

R¹, R², R^(1′) and R^(2′) are independently of each other a group offormula

wherein i is an integer from 1 to 10; R⁷⁰, R⁷¹ and R⁷² are independentlyof each other hydrogen or C₁-C₅₀alkyl; with the proviso that at leastone of the substituents R⁷⁰, R⁷¹ and R⁷² is different from hydrogen.

In a more preferred embodiment the present invention is directed topolymers, comprising a repeating unit of formula—[Ar³]_(c)—[Ar²]_(b)—[Ar¹]_(a)—Y(R¹)_(n1)(R²)_(n2)—[Ar^(1′)]_(a′)—[Ar^(2′)]_(b′)—[Ar^(3′)]_(c′)—  (I),wherein

a is 0, 1, or 2; a′ is 0, 1 or 2; b is 0, or 1; b′ is 0, or 1; c is 0,or 1; c′ is 0, or 1; preferably a is 0, 1, or 2, a′ is 0, 1 or 2; b is0; b′ is 0; c is 0; c′ is 0; more preferably a is 0, or 1; a′ is 0, or1; b is 0; b′ is 0; c is 0; c′ is 0;

Y(R¹)_(n1)(R²)_(n2) is a group of formula (IIIa), (IIIb), (IIId),(IIIe), (IIIh), or (IIIi),

Ar¹ and Ar^(1′) are independently of each other a group of formulaXIa-1, XIa-2, XIa-4, or XId, Ar², Ar^(2′), Ar³ and Ar^(3′) areindependently of each other a group of formula XIa-1, XIa-2, XIa-4, XId,or XIIIi-1,

R¹, R², R^(1′) and R^(2′) are independently of each other a group offormula (II), wherein i is an integer from 1 to 10; R⁷⁰, R⁷¹ and R⁷² areindependently of each other hydrogen or C₁-C₅₀alkyl; with the provisothat two of the substituents R⁷⁰, R⁷¹ and R⁷² are different fromhydrogen.

In an even more preferred embodiment the present invention is directedto polymers, comprising a repeating unit of formula—[Ar³]_(c)—[Ar²]_(b)—[Ar¹]_(a)—Y(R¹)_(n1)(R²)_(n2)—[Ar^(1′)]_(a′)—[Ar^(2′)]_(b′)—[Ar^(3′)]_(c′)—  (I),wherein

a is 0, 1, or 2, a′ is 0, 1 or 2; b is 0; b′ is 0; c is 0; c′ is 0;preferably a is 0, or 1; a′ is 0, or 1; b is 0; b′ is 0; c is 0; c′ is0;

Y(R¹)_(n1)(R²)_(n2) is a group of formula (IIIa), (IIIb), or (IIId),

Ar¹ and Ar^(1′) are independently of each other a group of formulaXIa-1, or XIa-4,

Ar², Ar^(2′), Ar³ and Ar^(3′) are independently of each other a group offormula XIa-1, XIa-4, or XIIIi-1,

R¹ and R² are independently of each other a group of formula (II),wherein i is an integer from 1 to 5; and R⁷⁰, R⁷¹ and R⁷² areindependently of each other hydrogen or C₁-C₃₆alkyl; with the provisothat two of the substituents R⁷⁰, R⁷¹ and R⁷² are different fromhydrogen.

Most preferred one of the substituents R⁷⁰, R⁷¹ and R⁷² is hydrogen andthe other two of the substituents R⁷⁰, R⁷¹ and R⁷² are C₁-C₃₆alkyl,especially C₆-C₂₄alkyl, very especially C₈-C₁₈alkyl.

Halogen can be F, Cl, Br and I.

C₁-C₄alkyl, C₁-C₁₀alkyl, C₁-C₂₅alkyl and C₁-C₅₀alkyl can be branched orunbranched. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl,n-(1-ethyl)propyl, n-hexyl, n-heptyl, n-octyl, n-(2-ethyl)hexyl,n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-undecyl, n-dodecyl,n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl,n-octadecyl, n-nonadecyl, n-icosyl (C₂₀), n-docosyl (C₂₂), n-tetracosyl(C₂₄), n-hexacosyl (C₂₆), n-octacosyl (C₂₈) and n-triacontyl (C₃₀).

C₂-C₈alkenyl, C₃-C₈alkenyl, C₂-C₂₅alkenyl, C₃-C₂₅alkenyl, C₂-C₅₀alkenyland C₃-C₅₀alkenyl can be branched or unbranched. Examples are vinyl,propenyl, cis-2-butenyl, trans-2-butenyl, 3-butenyl, cis-2-pentenyl,trans-2-pentenyl, cis-3-pentenyl, trans-3-pentenyl, 4-pentenyl,2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl, docenyl,linoleyl (C₁₈), linolenyl (C₁₈), oleyl (C₁₈), arachidonyl (C₂₀) anderucyl (C₂₂).

C₂-C₂₅alkynyl, C₃-C₂₅alkynyl, C₂-C₅₀alkynyl and C₃-C₅₀alkynyl can bebranched or unbranched. Examples are ethynyl, 2-propynyl, 2-butynyl,3-butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, undecynyl,dodecynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl,hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl and icosynyl (C₂₀).

Halogenated C₁-C₈alkyl and C₁-C₂₅alkyl (C₁-C₂₅haloalkyl) are aC₁-C₂₅alkyl group, where a part or all of the hydrogen atoms arereplaced by halogen atoms, such as, for example, CF₃.

C₁-C₂₅alkanoyl (C₂₋₁₈alkanoyl) refers to a group R^(w)—(C═O)—, withR^(w) is C₁₋₂₅alkyl (C₁₋₁₈alkyl). Specific examples thereof include anacetyl group, a n-propanoyl group, an isopropanoyl group, a n-butyroylgroup, and a tert-butyroyl group.

Examples of C₅-C₈cycloalkyl and C₅-C₁₂cycloalkyl are cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl.

Examples of C₆-C₁₄aryl and C₆-C₂₄aryl are phenyl,

C₆-C₁₄aryl or C₆-C₂₄aryl may be optionally further substituted with oneor more C₁-C₁₂alkyl, C₁-C₁₂alkoxy, or halogen, especially fluorine.C₆-C₁₄aryl or C₆-C₂₄aryl are preferably unsubstituted.

C₂-C₂₀heteroaryl is a monocyclic or polycyclic, such as dicyclic,tricyclic or tetracyclic, ring system, which comprise at least oneheteroaromatic ring, and which may also comprise non-aromatic rings,which may be substituted by ═O.

Examples of heteroaryl are

wherein R¹⁰⁰ and R¹⁰¹ are independently and at each occurrence selectedfrom the group consisting of H, C₁-C₂₀alkyl, C₂₋₂₀alkenyl, C₂₋₂₀alkynyl,C₅₋₈cycloalkyl, C₆₋₁₄aryl and C₂-C₂₀heteroaryl, or R¹⁰⁰ and R¹⁰¹, ifattached to the same atom, together with the atom, to which they areattached, form a 5 to 12 membered ring system. C₂-C₂₀heteroaryl may beoptionally further substituted with one or more C₁-C₁₂alkyl,C₁-C₁₂alkoxy, or halogen, especially fluorine. C₂-C₂₀heteroaryl ispreferably unsubstituted.

The 5 to 12 membered ring system can contain, in addition to the atom,to which R¹⁰⁰ and R¹⁰¹, respectively are attached, ring members selectedfrom the group consisting of CH₂, O, S and NR¹⁰², werein R¹⁰² is at eachoccurrence selected from the group consisting of H, C₁-C₁₀alkyl,C₃-C₁₀alkenyl and C₃-C₁₀alkynyl.

C₇-C₂₅aralkyl is typically benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl,α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl,ω-phenyl-dodecyl, ω-phenyl-octadecyl, ω-phenyl-eicosyl orω-phenyl-docosyl, preferably C₇-C₁₈aralkyl such as benzyl,2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl,ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl, andparticularly preferred C₇-C₁₂aralkyl such as benzyl, 2-benzyl-2-propyl,β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, orω,ω-dimethyl-ω-phenyl-butyl, in which both the aliphatic hydrocarbongroup and aromatic hydrocarbon group may be unsubstituted orsubstituted. Preferred examples are benzyl, 2-phenylethyl,3-phenylpropyl, naphthylethyl, naphthylmethyl, and cumyl.

C₁-C₂₅alkoxy groups (C₁-C₁₂alkoxy groups) are straight-chain or branchedalkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy,octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy,tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy andoctadecyloxy.

The compounds of formula

X³—[Ar³]_(c)—[Ar²]_(b)—[Ar¹]_(a)—Y(R¹)_(n1)(R²)_(n2)—[Ar^(1′)]_(a′)—[Ar^(2′)]_(b′)—[Ar^(3′)]_(c′)—X⁴(X) are new and form a further subject of the present invention, whereina, a′, b, b′, c, c′, Y, n1, n2, Ar², Ar^(2′), Ar³, Ar^(3′), R¹ and R²are defined above, or below, Ar¹ and A^(1′) are defined above, or below,

X³ and X⁴ are independently of each other hydrogen, halogen, ZnX¹²,—SnR²⁰⁷R²⁰⁸R²⁰⁹, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or differentand are H or C₁-C₆alkyl, wherein two radicals optionally form a commonring and these radicals are optionally branched or unbranched and X¹² isa halogen atom; or —OS(O)₂CF₃, —OS(O)₂-aryl, —OS(O)₂CH₃, —B(OH)₂,—B(OY¹)₂,

—BF₄Na, or —BF₄K, wherein Y¹ is independently in each occurrence aC₁-C₁₀alkyl group and Y² is independently in each occurrence anoptionally substituted C₂-C₁₀alkylene group, such as —CY³Y⁴—CY⁵Y⁶—, or—CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, Y¹¹ andY¹² are independently of each other hydrogen, or a C₁-C₁₀alkyl group,

especially —C(CH₃)₂C(CH₃)₂—, —CH₂C(CH₃)₂CH₂—, or —C(CH₃)₂CH₂C(CH₃)₂—,and Y¹³ and Y¹⁴ are independently of each other hydrogen, or aC₁-C₁₀alkyl group.

In a preferred embodiment the present invention is directed to compoundsof formula (X), wherein a is 0, 1, or 2; a′ is 0, 1, or 2; b is 0, 1, or2; b′ is 0, 1, or 2; c is 0, 1, or 2; c′ is 0, 1, or 2; more preferablya is 0, 1, or 2; a′ is 0, 1 or 2; b is 0, or 1; b′ is 0, or 1; c is 0,or 1; c′ is 0, or 1; even more preferably a is 0, 1, or 2, a′ is 0, 1 or2; b is 0; b′ is 0; c is 0; c′ is 0; most preferably a is 0, or 1; a′ is0, or 1; b is 0; b′ is 0; c is 0; c′ is 0; with the proviso that if Y isIIIa, a and a′ are not 0,

Y(R¹)_(n1)(R²)_(n2) is a group of formula (IIIa), (IIIb), (IIIc),(IIId), (IIIe), (IIIf), (IIIg), (IIIh), or (IIIi), Ar¹ and Ar^(1′) areindependently of each other a group of formula XIa-1, XIa-2, XIa-4, XIb,XId, XIi, XIm, or XIz-1,

Ar², Ar^(2′), Ar³ and Ar^(3′) are independently of each other a group offormula XIa-1, XIa-2, XIa-4, XIb, XId, XIi, XIm, XIx-1, XIx-2, XIx-3,XIx-5, XIz-1, XIIIa, XIIIb-1, XIIIb-2, XIIIe, XIIIi-1, or XIIIj,

R¹, R², R^(1′) and R^(2′) are independently of each other a group offormula

wherein i is an integer from 1 to 10; R⁷⁰, R⁷¹ and R⁷² are independentlyof each other hydrogen or C₁-C₅₀alkyl; with the proviso that at leastone of the substituents R⁷⁰, R⁷¹ and R⁷² is different from hydrogen.

In a more preferred embodiment the present invention is directed tocompounds of formula (X), wherein a is 0, 1, or 2; a′ is 0, 1 or 2; b is0, or 1; b′ is 0, or 1; c is 0, or 1; c′ is 0, or 1; preferably a is 0,1, or 2, a′ is 0, 1 or 2; b is 0; b′ is 0; c is 0; c′ is 0; morepreferably a is 0, or 1; a′ is 0, or 1; b is 0; b′ is 0; c is 0; c′ is0; with the proviso that if Y is IIIa, a and a′ are not 0,

Y(R¹)_(n1)(R²)_(n2) is a group of formula (IIIa), (IIIb), (IIId),(IIIe), (IIIh), or (IIIi), Ar¹ and Ar^(1′) are independently of eachother a group of formula XIa-1, XIa-2, XIa-4, or XId, Ar², Ar^(2′), Ar³and Ar^(3′) are independently of each other a group of formula XIa-1,XIa-2, XIa-4, XId, or XIIIi-1,

R¹, R², R^(1′) and R^(2′) are independently of each other a group offormula (II), wherein i is an integer from 1 to 10; R⁷⁰, R⁷¹ and R⁷² areindependently of each other hydrogen or C₁-C₅₀alkyl; with the provisothat two of the substituents R⁷⁰, R⁷¹ and R⁷² are different fromhydrogen.

In an even more preferred embodiment the present invention is directedto compounds of formula (X), wherein a is 0, 1, or 2, a′ is 0, 1 or 2; bis 0; b′ is 0; c is 0; c′ is 0; preferably a is 0, or 1; a′ is 0, or 1;b is 0; b′ is 0; c is 0; c′ is 0; with the proviso that if Y is IIIa, aand a′ are not 0,

Y(R¹)_(n1)(R²)_(n2) is a group of formula (IIIa), (IIIb), or (IIId), Ar¹and Ar^(1′) are independently of each other a group of formula XIa-1, orXIa-4, Ar², Ar^(2′), Ar³ and Ar^(3′) are independently of each other agroup of formula XIa-1, XIa-4, or XIIIi-1,

R¹ and R² are independently of each other a group of formula (II),wherein i is an integer from 1 to 5; and R⁷⁰, R⁷¹ and R⁷² areindependently of each other hydrogen or C₁-C₃₆alkyl; with the provisothat two of the substituents R⁷⁰, R⁷¹ and R⁷² are different fromhydrogen. Halogen can be F, Cl, Br and I.

X³ and X⁴ are preferably hydrogen, or halogen, more preferably H, Cl,Br, or I, more preferably H, Br, or I, most preferred H, or Br.

Examples of the compound of formula (X) are shown below:

More preferred are compounds of the formula I-1, I-2, I-5, I-6, I-9,I-10, I-13, I-14, I-21, I-22, I-23 and I-24 and even more preferred arecompounds of the formulae I-1, I-2, I-5, I-6, I-9, I-10, I-13 and I-14.Preferably, R¹, R², R^(1′) and R^(2′) are independently of each other agroup of formula

wherein i is an integer from 1 to 10; R⁷⁰, R⁷¹ and R⁷² are independentlyof each other hydrogen or C₁-C₅₀alkyl; with the proviso that at leastone of the substituents R⁷⁰, R⁷¹ and R⁷² is different from hydrogen.More preferably, R¹, R², R^(1′) and R^(2′) are independently of eachother a group of formula (II), wherein i is an integer from 1 to 10,especially 1 to 5; R⁷⁰, R⁷¹ and R⁷² are independently of each otherhydrogen or C₁-C₅₀alkyl; with the proviso that two of the substituentsR⁷⁰, R⁷¹ and R⁷² are different from hydrogen.

The synthesis of the compounds of formula (X) is described in moredetail on basis of a compound where Y is a group of formula

A compound of the formula

may be transformed into a desired product of the formula

wherein R¹ and R² are independently of each other a group of formula(II) by N-alkylation by heating a mixture of a compound of formula IXand potassium carbonate in dimethyl formamide followed by addition of

For example, a mixture of a compound of the formula (IX) indimethylformamide is treated at room temperature with a suitable base,e.g. K₂CO₃. Thereafter, the iodide of the formula

is added and the reaction mixture is heated to 50 to 100° C. for 2 to 24h. The obtained compound can be further brominated in analogy to aprocedure described in

WO2009/047104 to obtain a compound of formula

Alternatively, the compound of formula

can be obtained from a compound of formula

by alkylation, for example, via a procedure described in US2014/0264184.

The preparation of the compounds of formula (IX) is, for example,described in WO2009/047104, or can be done in analogy to the methodsdescribed therein.

The compounds of formula

can be obtained, for example, by reacting a compound of formula

with N-bromosuccinimide, Br₂, or I₂ in a solvent, like dichloromethane,for example, in the presence of imidazole and/or triphenylphosphine.

The compound of formula

can be synthesized via the following route (Wittig reaction):

R⁷⁰ is preferably hydrogen and R⁷¹ and R⁷² are preferably C₁-C₃₆alkyl, jis i-1, R²⁰⁰ is in each occurence C₁-C₁₂alkyl or both substituents R²⁰⁰together form a group —(CH₂)_(m)— and m is 2 to 4.

Alternatively, compounds of formula

can be obtained by dehydration of a compound of formula

in a solvent, like toluene, in the presence of an acid, likep-toluenesulfonic, at elevated temperature, for example, at refluxtemperature. If R⁷¹ and/or R⁷² contain α-hydrogens in relation to thecarbon atom where R⁷¹ and/or R⁷² are attached, isomeric mixtures can beobtained. An example of the synthesis of an isomeric mixture is givenbelow.

R⁷⁰ is preferably hydrogen and R⁷¹ and R⁷² are preferably C₁-C₃₆alkyl.

In case of the following dihydroxy compound

the dehydration process may lead to the following three isomers:

(i=3, R⁷⁰ is hydrogen, R⁷¹ is C₁₀alkyl, R⁷² is C₁₀alkyl)

(i=4, R⁷⁰ is C₁₀alkyl, R⁷¹ is C₉alkyl, R⁷² is hydrogen) and

(i=4, R⁷⁰ is C₁₀alkyl, R⁷¹ is hydrogen, R⁷² is C₉alkyl). Hence, allproducts derived from such an isomeric mixture may contain isomers. Thatis, the side chains, R¹, R², R^(1′) and R^(2′), may consist of differentisomers.

The diols of formula

are commercially available, or can be produced, for example, in analogyto methods described in US2014/0011973 WO2007/091009, as shown inExample 1 of the present application.

Polymers made with monomers containing the group of formula (II) showhigh mobilities and high solubility which is important for printedelectronic applications.

Polymers of formula -[[A]-[COM]_(n3)]n- (V′), can be obtained, forexample, by the Suzuki reaction. The condensation reaction ofdi-boronate and a di-halogenide, especially a dibromide, commonlyreferred to as the “Suzuki reaction”, is tolerant of the presence of avariety of organic functional groups as reported by N. Miyaura and A.Suzuki in Chemical Reviews, Vol. 95, pp. 457-2483 (1995).

To prepare polymers corresponding to formula -[[A]-[COM]_(n3)]n- (V′),dihalogenides corresponding to formula X^(11′)-A-X^(11′) are reactedwith diboronic acids, or diboronates corresponding to formulaX¹¹-[COM]_(n3)-X¹¹; or diboronic acids, or diboronates corresponding toformula X¹¹-A-X¹¹ are reacted with dihalogenides of formulaX^(11′)-[COM]_(n3)-X^(11′), wherein X^(11′) is independently in eachoccurrence Cl, Br, or I, and X¹¹ is independently in each occurrence—B(OH)₂, —B(OY¹)₂,

wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group andY² is independently in each occurrence a C₂-C₁₀alkylene group, such as—CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷,Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or aC₁-C₁₀alkyl group, especially —C(CH₃)₂C(CH₃)₂—, —CH₂C(CH₃)₂CH₂—, or—C(CH₃)₂CH₂C(CH₃)₂—, and Y¹³ and Y¹⁴ are independently of each otherhydrogen, or a C₁-C₁₀alkyl group, in a solvent and in the presence of acatalyst, such as, for example, under the catalytic action of Pd andtriphenylphosphine.

Preferred catalysts are2-dicyclohexylphosphino-2′,6′-di-alkoxybiphenyl/palladium(II) acetates,tri-alykl-phosphonium salts/palladium (0) derivatives andtri-alkylphosphine/palladium (0) derivatives. Especially preferredcatalysts are 2-dicyclohexylphosphino-2′,6′-di-methoxybiphenyl(sPhos)/palladium(II)acetate and, tri-tert-butylphosphoniumtetrafluoroborate ((t-Bu)₃P*HBF₄)/tris(dibenzylideneacetone) dipalladium(0) (Pd₂(dba)₃) and tri-tert-butylphosphine(t-Bu)₃P/tris(dibenzylideneacetone) dipalladium (0) (Pd₂(dba)₃). Thereaction is typically conducted at about 0° C. to 180° C. in an aromatichydrocarbon solvent such as toluene, xylene. Other solvents such asdimethylformamide, dioxane, dimethoxyethan and tetrahydrofuran can alsobe used alone, or in mixtures with an aromatic hydrocarbon. An aqueousbase, preferably sodium carbonate or bicarbonate, potassium phosphate,potassium carbonate or bicarbonate is used as activation agent for theboronic acid, boronate and as the HBr scavenger. A polymerizationreaction may take 0.2 to 100 hours. Organic bases, such as, for example,tetraalkylammonium hydroxide, and phase transfer catalysts, such as, forexample TBAB, can promote the activity of the boron (see, for example,Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 andreferences cited therein). Other variations of reaction conditions aregiven by T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994)5034-5037; and M. Remmers, M. Schulze, and G. Wegner in Macromol. RapidCommun. 17 (1996) 239-252. Control of molecular weight is possible byusing either an excess of dibromide, diboronic acid, or diboronate, or achain terminator.

A particularly preferred process is described in WO2010/136352.According to the process described in WO2010/136352 the polymerisationis carried out in presence of

a) a catalyst/ligand system comprising a palladium catalyst and aspecific organic phosphine, or phosphonium compound,

b) a base,

c) a solvent or a mixture of solvents. Preferred organic phosphines areselected from trisubstituted phosphines of formula

Cpd. R^(1″) R³⁰⁵ R³⁰⁶ R³⁰³ R³⁰⁴ A-1

H H H H A-2 cyclohexyl H H H H A-3 phenyl H H H H A-4 adamantyl H H H HA-5 cyclohexyl —OCH₃ H H H A-6 cyclohexyl ¹⁾ ¹⁾ H H A-7

¹⁾ ¹⁾ H H A-8 phenyl ¹⁾ ¹⁾ H H A-9 adamantyl ¹⁾ ¹⁾ H H A-10 cyclohexyl HH ²⁾ ²⁾ A-11

H H ²⁾ ²⁾ A-12 phenyl H H ²⁾ ²⁾ A-13 adamantyl H H ²⁾ ²⁾

Examples of preferred catalysts include the following compounds:

palladium(II) acetylacetonate, palladium(0) dibenzylidene-acetonecomplexes, palladium(II) propionate,

Pd₂(dba)₃: [tris(dibenzylideneacetone) dipalladium(0)],

Pd(dba)₂: [bis(dibenzylideneacetone) palladium(0)],

Pd(PR₃)₂, wherein PR₃ is a trisubstituted phosphine of formula VI,

Pd(OAc)₂: [palladium(II) acetate], palladium(II) chloride, palladium(II)bromide, lithium tetrachloropalladate(II),

PdCl₂(PR₃)₂; wherein PR₃ is a trisubstituted phosphine of formula VI;palladium(0) diallyl ether complexes, palladium(II) nitrate,

PdCl₂(PhCN)₂: [dichlorobis(benzonitrile) palladium(II)],

PdCl₂(CH₃CN): [dichlorobis(acetonitrile) palladium(II)], and

PdCl₂(COD): [dichloro(1,5-cyclooctadiene) palladium(II)].

Especially preferred are PdCl₂, Pd₂(dba)₃, Pd(dba)₂, Pd(OAc)₂, orPd(PR₃)₂. Most preferred are Pd₂(dba)₃ and Pd(OAc)₂.

The palladium catalyst is present in the reaction mixture in catalyticamounts. The term “catalytic amount” refers to an amount that is clearlybelow one equivalent of the (hetero)aromatic compound(s), preferably0.001 to 5 mol- %, most preferably 0.001 to 1 mol- %, based on theequivalents of the (hetero)aromatic compound(s) used.

The amount of phosphines or phosphonium salts in the reaction mixture ispreferably from 0.001 to 10 mol- %, most preferably 0.01 to 5 mol- %,based on the equivalents of the (hetero)aromatic compound(s) used. Thepreferred ratio of Pd:phosphine is 1:4.

The base can be selected from all aqueous and nonaqueous bases and canbe inorganic, or organic. It is preferable that at least 1.5 equivalentsof said base per functional boron group is present in the reactionmixture. Suitable bases are, for example, alkali and alkaline earthmetal hydroxides, carboxylates, carbonates, fluorides and phosphatessuch as sodium and potassium hydroxide, acetate, carbonate, fluoride andphosphate or also metal alcoholates. It is also possible to use amixture of bases. The base is preferably a lithium salt, such as, forexample, lithium alkoxides (such as, for example, lithium methoxide andlithium ethoxide), lithium hydroxide, carboxylate, carbonate, fluorideand/or phosphate.

The at present most preferred base is aqueous LiOHxH₂O (monohydrate ofLiOH) and (waterfree) LiOH.

The reaction is typically conducted at about 0° C. to 180° C.,preferably from 20 to 160° C., more preferably from 40 to 140° C. andmost preferably from 40 to 120° C. A polymerization reaction may take0.1 to 100 hours, especially 0.2 to 100 hours.

The solvent is for example selected from toluene, xylenes, anisole, THF,2-methyltetrahydrofuran, dioxane, chlorobenzene, fluorobenzene orsolvent mixtures comprising one or more solvents like e.g. THF/tolueneand optionally water. Most preferred is THF, or THF/water.

In a preferred embodiment of the present invention the solvent is THF,the base is LiOH*H₂O and the reaction is conducted at reflux temperatureof THF (about 65° C.).

Advantageously, the polymerisation is carried out in presence of

a) palladium(II) acetate, or Pd₂(dba)₃,(tris(dibenzylideneacetone)dipalladium(0)) and an organic phosphine A-1to A-13,

b) LiOH, or LiOHxH₂O; and

c) THF, and optionally water. If the monohydrate of LiOH is used, nowater needs to be added.

Preferably the polymerization reaction is conducted under inertconditions in the absence of oxygen. Nitrogen and more preferably argonare used as inert gases.

The process described in WO2010/136352 is suitable for large-scaleapplications, is readily accessible and convert starting materials tothe respective polymers in high yield, with high purity and highselectivity. If desired, a monofunctional aryl halide or aryl boronatemay be used as a chain-terminator in such reactions, which will resultin the formation of a terminal aryl group.

It is possible to control the sequencing of the monomeric units in theresulting copolymer by controlling the order and composition of monomerfeeds in the Suzuki reaction.

Alternative preparation methods for the polymers of the presentinvention are illustrated in more detail below.

The polymers of the present invention can also be sythesized by theStille coupling (see, for example, Babudri et al, J. Mater. Chem., 2004,14, 11-34; J. K. Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508).

To prepare polymers corresponding to formula -[[A]-[COM]_(n3)]n- (V′),dihalogenides of formula X^(11′)-A-X11′ are reacted with compounds offormula X²¹-[COM]_(n3)-X²¹; or dihalogenides of formulaX^(11′)-[COM]_(n3)-X^(11′) are reacted with compounds of formulaX²¹-A-X²¹, wherein X²¹ is a group —SnR²⁰⁷R²⁰⁸ R²⁰⁹ and X^(11′) is asdefined above, in an inert solvent at a temperature in range from 0° C.to 200° C. in the presence of a palladium-containing catalyst, whereinR²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or different and are H or C₁-C₆alkyl,wherein two radicals optionally form a common ring and these radicalsare optionally branched or unbranched. It must be ensured here that thetotality of all monomers used has a highly balanced ratio of organotinfunctions to halogen functions. In addition, it may prove advantageousto remove any excess reactive groups at the end of the reaction byend-capping with monofunctional reagents. In order to carry out theprocess, the tin compounds and the halogen compounds are preferablyintroduced into one or more inert organic solvents and stirred at atemperature of from 0 to 200° C., preferably from 30 to 170° C. for aperiod-from 1 hour to 200 hours, preferably from 5 hours to 150 hours.The crude product can be purified by methods known to the person skilledin the art and appropriate for the respective polymer, for example,Soxhlet extraction, repeated re-precipitation or even by dialysis.

Suitable organic solvents for the process described are, for example,ethers, for example diethyl ether, dimethoxyethane, diethylene glycoldimethyl ether, tetrahydrofuran, dioxane, dioxolane, diisopropyl etherand tert-butyl methyl ether, hydrocarbons, for example hexane,isohexane, heptane, cyclohexane, benzene, toluene and xylene, alcohols,for example methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol,1-butanol, 2-butanol and tert-butanol, ketones, for example acetone,ethyl methyl ketone and isobutyl methyl ketone, amides, for exampledimethylformamide (DMF), dimethylacetamide and N-methylpyrrolidone,nitriles, for example acetonitrile, propionitrile and butyronitrile, andmixtures thereof.

The palladium and phosphine components should be selected analogously tothe description for the Suzuki variant.

Alternatively, the polymers of the present invention can also besynthesized by the Negishi reaction using zinc reagents A-(ZnX²²)₂,wherein X²² is halogen and halides, and [COM]_(n3)-(X²³)₂, wherein X²³is halogen or triflate, or using [COM]_(n3)-(X²²)₂, and A-(ZnX²³)₂.Reference is, for example, made to E. Negishi et al., Heterocycles 18(1982) 117-22.

Alternatively, the polymers of the present invention can also besynthesized by the Hiyama reaction using organosilicon reagentsA-(SiR²¹⁰R²¹¹R²¹²)₂, wherein R²¹⁰, R²¹¹ and R²¹² are identical ordifferent and are halogen, or C₁-C₆alkyl, and [COM]_(n3)-(X²³)₂, whereinX²³ is halogen or triflate, or using A-(X²³)₂ and[COM]_(n3)-(SiR²¹⁰R²¹¹R²¹²)₂. Reference is, for example, made to T.Hiyama et al., Pure Appl. Chem. 66 (1994) 1471-1478 and T. Hiyama etal., Synlett (1991) 845-853.

Alternatively, the polymers of the present invention can also besynthesized by a direct arylation polymerization method described inMacromolecules 2015, 48, 6978-6986.

In another embodiment the present invention is directed to homopolymersof the type (A)_(n). Homopolymers of the type (A)_(n) can be obtainedvia Yamamoto coupling of dihalides X^(11′)-A-X^(11′), where X^(11′) ishalogen, especially Cl, Br, or I, very especially Br. Alternativelyhomopolymers of the type (A)_(n) can be obtained via oxidativepolymerization of units X^(11′)-A-X^(11′), where X^(11′) is hydrogen,e.g. with FeCl₃ as oxidizing agent.

A mixture containing a polymer of the present invention results in asemi-conducting layer comprising a polymer of the present invention(typically 5% to 99.9999% by weight, especially 20 to 85% by weight) andat least another material. The other material can be, but is notrestricted to a fraction of the same polymer of the present inventionwith different molecular weight, another polymer of the presentinvention, a semi-conducting polymer, organic small molecules, carbonnanotubes, a fullerene derivative, inorganic particles (quantum dots,quantum rods, quantum tripods, TiO₂, ZnO etc.), conductive particles(Au, Ag etc.), insulator materials like the ones described for the gatedielectric (PET, PS etc.). The polymers of the present invention can beblended with small molecules described, for example, in WO2009/047104,WO2010108873, WO09/047104, U.S. Pat. No. 6,690,029, WO2007082584, andWO2008107089.

The polymer can contain a small molecule, or a mixture of two, or moresmall molecule compounds.

Accordingly, the present invention also relates to an organicsemiconductor material, layer or component, comprising a polymeraccording to the present invention.

The polymers of the invention can be used as the semiconductor layer insemiconductor devices. Accordingly, the present invention also relatesto semiconductor devices, comprising a polymer of the present invention,or an organic semiconductor material, layer or component. Thesemiconductor device is especially an organic photovoltaic (PV) device(solar cell), a photodiode, or an organic field effect transistor.

The polymers of the invention can be used alone or in combination as theorganic semiconductor layer of the semiconductor device. The layer canbe provided by any useful means, such as, for example, vapor deposition(for materials with relatively low molecular weight) and printingtechniques. The compounds of the invention may be sufficiently solublein organic solvents and can be solution deposited and patterned (forexample, by spin coating, dip coating, ink jet printing, gravureprinting, blading, slot die coating, spraying, flexo printing, offsetprinting, screen printing, microcontact (wave)-printing, drop or zonecasting, or other known techniques).

The polymers of the invention can be used in integrated circuitscomprising a plurality of OTFTs, as well as in various electronicarticles. Such articles include, for example, radio-frequencyidentification (RFID) tags, backplanes for flexible displays (for usein, for example, personal computers, cell phones, or handheld devices),smart cards, medical devices, memory devices, sensors (e.g. light-,image-, bio-, chemo-, mechanical- or temperature sensors), especiallyphotodiodes, or security devices and the like.

The polymers of the present invention are typically used as organicsemiconductors in form of thin organic layers or films, preferably lessthan 30 microns thick. Typically the semiconducting layer of the presentinvention is at most 1 micron (=1 μm) thick, although it may be thickerif required. For various electronic device applications, the thicknessmay also be less than about 1 micron thick. For example, for use in anOFET the layer thickness may typically be 100 nm or less. The exactthickness of the layer will depend, for example, upon the requirementsof the electronic device in which the layer is used.

For example, the active semiconductor channel between the drain andsource in an OFET may comprise a polymer of the present invention. OFETshave been described in the literature in many different architecturesand specifications known to the person skilled in the art. Reference ismade to all these OFETs, replacing their semiconducting material in partor completely with a semiconducting material of the present application.

Typically, an organic field effect transistor comprises a dielectriclayer, a semiconducting layer and a substrate. In addition, an organicfield effect transistor usually comprises a gate electrode andsource/drain electrodes.

An OFET device according to the present invention preferably comprises:

-   -   a source electrode,    -   a drain electrode,    -   a gate electrode,    -   a semiconducting layer,    -   one or more gate insulator layers, and    -   optionally a substrate, wherein the semiconductor layer        comprises one or more polymers of the present invention.

The semiconducting layer can have a thickness of 5 to 500 nm, preferablyof 10 to 100 nm, more preferably of 20 to 50 nm.

The insulator layer comprises a dielectric material. The dielectricmaterial can be silicon dioxide or aluminium oxide, or, an organicpolymer such as polystyrene (PS), poly(methylmethacrylate) (PMMA),poly(4-vinylphenol) (PVP), poly(vinyl alcohol) (PVA), benzocyclobutene(BCB), or polyimide (PI). The insulator layer can have a thickness of 10to 2000 nm, preferably of 50 to 1000 nm, more preferably of 100 to 800nm.

The insulator layer can in addition to the dielectric material comprisea self-assembled monolayer of organic silane derivates or organicphosphoric acid derivatives. An example of an organic silane derivativeis octyltrichlorosilane. An example of an organic phosphoric acidderivative is octyldecylphosphoric acid. The self-assembled monolayercomprised in the insulator layer is usually in contact with thesemiconducting layer.

The source/drain electrodes can be made from any suitable organic orinorganic source/drain material. Examples of inorganic source/drainmaterials are gold (Au), silver (Ag) or copper (Cu), as well as alloyscomprising at least one of these metals. The source/drain electrodes canhave a thickness of 1 to 100 nm, preferably from 20 to 70 nm.

The gate electrode can be made from any suitable gate material such ashighly doped silicon, aluminium (Al), tungsten (W), indium tin oxide orgold (Au), or alloys comprising at least one of these metals. The gateelectrode can have a thickness of 1 to 200 nm, preferably from 5 to 100nm.

The substrate can be any suitable substrate such as glass, or a plasticsubstrate such as polyethersulfone, polycarbonate, polysulfone,polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).Depending on the design of the organic field effect transistor, the gateelectrode, for example highly doped silicon can also function assubstrate.

The gate, source and drain electrodes and the insulating andsemiconducting layer in the OFET device may be arranged in any sequence,provided that the source and drain electrode are separated from the gateelectrode by the insulating layer, the gate electrode and thesemiconductor layer both contact the insulating layer, and the sourceelectrode and the drain electrode both contact the semiconducting layer.

Preferably, the OFET comprises an insulator having a first side and asecond side, a gate electrode located on the first side of theinsulator, a layer comprising a polymer of the present invention locatedon the second side of the insulator, and a drain electrode and a sourceelectrode located on the polymer layer.

The OFET device can be a top gate device or a bottom gate device.

Suitable structures and manufacturing methods of an OFET device areknown to the person skilled in the art and are described in theliterature, for example in WO03/052841.

The semiconducting layer comprising a polymer of the present inventionmay additionally comprise at least another material. The other materialcan be, but is not restricted to another polymer of the presentinvention, a semi-conducting polymer, a polymeric binder, organic smallmolecules different from a polymer of the present invention, carbonnanotubes, especially semiconducting carbon nanotubes, a fullerenederivative, inorganic particles (quantum dots, quantum rods, quantumtripods, TiO₂, ZnO etc.), conductive particles (Au, Ag etc.), andinsulator materials like the ones described for the gate dielectric(PET, PS etc.). As stated above, the semiconductive layer can also becomposed of a mixture of one or more polymers of the present inventionand a polymeric binder. The ratio of the polymers of the presentinvention to the polymeric binder can vary from 5 to 95 percent.Preferably, the polymeric binder is a semicristalline polymer such aspolystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP)and polymethylmethacrylate (PMMA). With this technique, a degradation ofthe electrical performance can be avoided (cf. WO2008/001123A1).

The polymers of the present invention are advantageously used in organicphotovoltaic (PV) devices (solar cells). Accordingly, the inventionprovides PV devices comprising a polymer according to the presentinvention. A device of this construction will also have rectifyingproperties so may also be termed a photodiode. Photoresponsive deviceshave application as solar cells which generate electricity from lightand as photodetectors which measure or detect light.

The PV device comprise in this order:

(a) a cathode (electrode),

(b) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,

(c) a photoactive layer,

(d) optionally a smoothing layer,

(e) an anode (electrode),

(f) a substrate.

The photoactive layer comprises the polymers of the present invention.Preferably, the photoactive layer is made of a conjugated polymer of thepresent invention, as an electron donor and an acceptor material, like afullerene, particularly a functionalized fullerene PCBM, as an electronacceptor. As stated above, the photoactive layer may also contain apolymeric binder. The ratio of the polymers of formula (I) to thepolymeric binder can vary from 5 to 95 percent. Preferably, thepolymeric binder is a semicristalline polymer such as polystyrene (PS),high-density polyethylene (HDPE), polypropylene (PP) andpolymethylmethacrylate (PMMA).

For heterojunction solar cells the active layer comprises preferably amixture of a polymer of the present invention and a fullerene, such as[60]PCBM (=6,6-phenyl-C₆₁-butyric acid methyl ester), or [70]PCBM, in aweight ratio of 1:1 to 1:3. The fullerenes useful in this invention mayhave a broad range of sizes (number of carbon atoms per molecule). Theterm fullerene as used herein includes various cage-like molecules ofpure carbon, including Buckminsterfullerene (C₆₀) and the related“spherical” fullerenes as well as carbon nanotubes. Fullerenes may beselected from those known in the art ranging from, for example,C₂₀-C₁₀₀₀. Preferably, the fullerene is selected from the range of C₆₀to C₉₆. Most preferably the fullerene is C₆₀ or C₇₀, such as [60]PCBM,or [70]PCBM. It is also permissible to utilize chemically modifiedfullerenes, provided that the modified fullerene retains acceptor-typeand electron mobility characteristics. The acceptor material can also bea material selected from the group consisting of any semi-conductingpolymer, such as, for example, a polymer of the present invention,provided that the polymers retain acceptor-type and electron mobilitycharacteristics, organic small molecules, carbon nanotubes, inorganicparticles (quantum dots, quantum rods, quantum tripods, TiO₂, ZnO etc.).

The photoactive layer is made of a polymer of the present invention asan electron donor and a fullerene, particularly functionalized fullerenePCBM, as an electron acceptor. These two components are mixed with asolvent and applied as a solution onto the smoothing layer by, forexample, the spin-coating method, the drop casting method, theLangmuir-Blodgett (“LB”) method, the ink jet printing method and thedripping method. A squeegee or printing method could also be used tocoat larger surfaces with such a photoactive layer. Instead of toluene,which is typical, a dispersion agent such as chlorobenzene is preferablyused as a solvent. Among these methods, the vacuum deposition method,the spin-coating method, the ink jet printing method and the castingmethod are particularly preferred in view of ease of operation and cost.

In the case of forming the layer by using the spin-coating method, thecasting method and ink jet printing method, the coating can be carriedout using a solution and/or dispersion prepared by dissolving, ordispersing the composition in a concentration of from 0.01 to 90% byweight in an appropriate organic solvent such as benzene, toluene,xylene, tetrahydrofurane, methyltetrahydrofurane, N,N-dimethylformamide,acetone, acetonitrile, anisole, dichloromethane, dimethylsulfoxide,chlorobenzene, 1,2-dichlorobenzene and mixtures thereof.

The photovoltaic (PV) device can also consist of multiple junction solarcells that are processed on top of each other in order to absorb more ofthe solar spectrum. Such structures are, for example, described in App.Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006)and WO2004/112161.

The PV device can also be processed on a fiber as described, forexample, in US20070079867 and US 20060013549.

The following examples are included for illustrative purposes only anddo not limit the scope of the claims. Unless otherwise stated, all partsand percentages are by weight.

Weight-average molecular weight (Mw) and polydispersity (Mw/Mn=PD) aredetermined by High Temperature Gel Permeation Chromatography (HT-GPC)[Apparatus: GPC PL 220 from Polymer laboratories (Church Stretton, UK;now Varian) yielding the responses from refractive index (RI),Chromatographic conditions: Column: 3 “PLgel Olexis” column from PolymerLaboratories (Church Stretton, UK); with an average particle size of 13ìm (dimensions 300×8 mm I.D.) Mobile phase: 1,2,4-trichlorobenzenepurified by vacuum distillation and stabilised by butylhydroxytoluene(BHT, 200 mg/I), Chromatographic temperature: 150° C.; Mobile phaseflow: 1 ml/min; Solute concentration: about 1 mg/ml; Injection volume:200 ìl; Detection: RI, Procedure of molecular weight calibration:Relative calibration is done by use of a set of 10 polystyrenecalibration standards obtained from Polymer Laboratories (ChurchStretton, UK) spanning the molecular weight range from 1′930′000Da-5′050 Da, i. e., PS 1′930′000, PS 1′460′000, PS 1′075′000, PS560′000, PS 330′000, PS 96′000, PS 52′000, PS 30′300, PS 10′100, PS5′050 Da. A polynomic calibration is used to calculate the molecularweight.

All polymer structures given in the examples below are idealizedrepresentations of the polymer products obtained via the polymerizationprocedures described. If more than two components are copolymerized witheach other sequences in the polymers can be either alternating or randomdepending on the polymerisation conditions. All experiments are carriedout in protective gas atmosphere. The percentages and ratios mentionedin the examples below—unless stated otherwise—are % by weight and weightratios.

EXAMPLES Example 1 a) Synthesis of the Diol 1

4.55 g of δ-valerolactone [542-28-9] dissolved in 45 ml of diethyletherare added under stirring dropwise to 100 ml of a 1 M Grignard-solutionof decyl-magnesium-bromide (in diethylether) [17049-50-2] at roomtemperature. The reaction mixture is then refluxed over night. Thereaction mixture is then cooled to 0° C. and carefully quenched by theaddition of 100 ml water, followed by the addition of 200 ml ofsaturated ammonium chloride solution. The layers are separated and theaqueous layer is once more extracted with ethylacetate. The combinedorganic layers are washed with brine and water, and are then dried overMgSO₄. After filtration and evaporation of the solvents, crude diol 1 isobtained. The crude material is used directly in the next step. ¹H-NMRdata (ppm, CDCl₃) correspond: 3.66 2H t, 1.63-1.52 2H m, 1.52-1.38 6H m,1.38-1.20 34H m, 0.90 6H t.

b) Synthesis of the Olefinic Alcohol 2 Via Dehydration

20.5 g of the crude diol 1 is dissolved in 350 ml of toluene. 0.39 g ofpara-toluenesulfonic acid are added and the reaction mixture is refluxedover night in a water separator. The reaction mixture is then cooled toroom temperature and washed with water. The organic phase is dried overMgSO₄ and filtered and the solvent is evaporated to give the crudecolorless olefinic compound 2 as isomeric mixture. The crude material isused directly in the next step. ¹H-NMR data (ppm, CDCl₃) correspond:5.14 1H broad t, 3.66 2H t, 2.08-1.94 6H m, 1.68-1.55 2H m, 1.55-1.2232H m, 0.91 6H t;

For the dehydration product only one possible isomer is drawn. Differentpossible isomers can be obtained during this dehydration process, whereall isomers form a mixture 2 containing different R—OH, wherein

c) Synthesis of the Olefinic Alkylating Agent 3

4.01 g of imidazole and 15.45 g of triphenylphosphine are dissolved in200 ml of dichloromethane under argon and cooled to 0° C. Then 14.95 gof iodine are added. After stirring for 15 minutes, 18 g of compound 2is added. The temperature is then rised to room temperature and themixture is stirred for 4 hours. The dichloromethane is evaporated andthe reminder is filtered with heptane over a silica plug. After theremoval of the heptane, crude compound 3 is obtained as isomeric mixtureR-I. The crude material is used directly in the next step.

d) Synthesis of the Alkylated DPP 4

6.14 g of the DPP-pigment [777079-55-7] is suspended in 150 ml drydimethylformamide together with 5.56 g of K₂CO₃ under nitrogen. Then 16g of crude compound mixture 3 are added and the mixture is heated to 90°C. and stirred overnight. After cooling 200 ml of water are added andthe product is extracted with toluene. The toluene phase is washed withwater, dried over MgSO₄, filtered and evaporated to give crude compound4 as isomeric mixture. The product is purified via column chromatographyover silica gel, to remove e.g. mono-alkylated product. ¹H-NMR data 300MHz (ppm, CDCl₃): 8.71 2H d, 7.25 2H d, 5.19-5.10 2H m, 4.01 4H t,2.19-1.95 12H m, 1.85-1.22 68H m, 0.90 12H t; mass spectrum corresponds.

e) Co-Polymerization of DPP 4 to the Polymer 5

1 g of DPP compound 4 and 291 mf of the boronicacidester [175361-81-6]are mixed together with 7.8 mg of palladium(II)acetat, 46.7 mg2-(di-tert-butylphosphino)-1-phenylindol [740815-37-6] and 217.9 mgLiOH.H₂O in 15 ml of degassed tetrahydrofuran under argon. The wholereaction mixture is stirred and the temperature rised to refluxtemperature. The reaction mixture is refluxed for 1.5 hours. Thereaction mixture is then cooled to room temperature and 40 ml of awater-methanol mixture is added to precipitate the polymer of structure5 (P1). The mixture is filtered and the residual polymer is washed withwater and dryed. The polymer is then extracted in a Soxhlet equipmentwith heptane, and then tetrahydrofuran. The tetrahydrofuran fraction isanalyzed by high temperature GPC (1,2,4-trichlorobenzene at 150° C.). Mwis 31′056 g/mol, PDI is 1.76.

Application Example 1 Fabrication and Electrical Characterization of anOrganic Field-Effect Transistor (OFET) Based on Compound P1 Preparationof Back-Contact, Top-Gate FETs

Compound P1 is dissolved at a concentration of 0.75 wt % indichlorobenzene and subsequently coated onto a PET-substrate withlithographically prepatterned gold contacts, serving as source and draincontact of the FET. 100 μl of the formulation is coated by a standardblade coater yielding a homogenous layer of the semiconductor over theentire substrate. After the coating is completed, the substrate isimmediately transferred onto a preheated hotplate and heated for 30 s at90° C. Next the gate dielectric layer consisting of polystyrene 4 wt %dissolved in PGMEA is spincoated on top of the organic semiconductor(2500 rpm, 30 s). After spincoating, the substrate is again transferredto the hotplate and annealed for another 5 Min at 100° C. The thicknessof the dielectric layer is 430 nm measured by profilometer. Finally 50nm thick shadow-mask patterned gold gate electrodes are deposited byvacuum evaporation to complete FETs in the BCTG-configuration.

Electrical Characterization

FIG. 1 show representative transfer characteristics of an FET fabricatedfrom compound P1 with V_(GS)=10 V to −30 V at 0.5V step size withV_(DS)=−30V. Drain current (black solid curve), Gate current (dottedgrey curve), Square root of drain current (grey solid curve), and fittedslope of square root (dashed black curve).

The mobility μ is calculated from the root representation of thetransfer characteristic curve (solid grey curve) calculated in thesaturation region. The slope m is determined from the dashed black linein FIG. 1. The dashed black line in FIG. 1 is fitted to a region of thesquare root representation of the drain current ID such that a goodcorrelation to the linear slope of the root representation is obtained.

The threshold voltage U_(Th) can be taken from the intersection of blackdashed line in FIG. 1 with the X-axis portion (V_(GS)).

In order to calculate the electrical properties of the OFET, thefollowing equations are employed:

${\mu = \frac{m^{2}*2L}{C_{G}*W}}\mspace{20mu}{C_{G} = {ɛ_{0}*ɛ_{r}\frac{1}{d}}}\mspace{14mu}{U_{Th} = {{- 1}*\frac{m}{b}}}\mspace{14mu}{{{ON}/{OFF}} = \frac{I_{D}\max}{I_{D}\min}}$where ε₀ is the vacuum permittivity of 8.85×10⁻¹² As/Vm. ε_(r)=2.6 forpolystyrene and d=430 nm is the thickness of the dielectric. With thechannel length L=200 μm and the channel width W=4000 μm.

The following mobilities, threshold voltage and ON/OFF ratio have beencalculated for the respective compound from an average of 4 TFTs:

Field-effect mobility Threshold voltage ON/OFF Compound μ [cm²/Vs]U_(TH) [V] ratio P1 0.18 −0.6 3.6E4

The invention claimed is:
 1. A polymer, comprising a repeating unit offormula (I):—[Ar³]_(c)—[Ar²]_(b)—[Ar¹]_(a)—Y(R¹)_(n1)(R²)_(n2)—[Ar^(1′)]_(a′),—[Ar^(2′)]_(b′), —[Ar^(3′)]_(c′)—  (I), wherein a is 0, 1, 2, or 3; a′is 0, 1, 2, or 3; b is 0, 1, 2, or 3; b′ is 0, 1, 2, or 3; c is 0, 1, 2,or 3; c′ is 0, 1, 2, or 3; n1 is 1, or 2; n2 is 1, or 2; Y is a bivalentheterocyclic group, or ring system, which may optionally be substituted;Ar¹, Ar^(1′), Ar², Ar^(2′), Ar³ and Ar^(3′) are independently of eachother a C₆-C₂₄arylen group, which can optionally be substituted, or aC₂-C₂₀heteroarylen group, which can optionally be substituted; R¹ and R²in each occurrence are independently of each other hydrogen,C₅-C₁₂cycloalkyl, COR³⁸, C₁-C₅₀alkyl, C₃-C₅₀alkenyl, or C₃-C₅₀alkynyl,which can optionally be substituted one or more times with C₁-C₁₂alkoxy,halogen, C₅-C₈cycloalkyl, cyano, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or asilyl group; and/or can optionally be further interrupted by one or more—O—, —S—, —NR³⁹—, —CONR³⁹—, —NR³⁹CO—, —COO—, —CO—, or —OCO—, or a groupof formula:

i is an integer from 1 to 18; R⁷⁰, R⁷¹ and R⁷² are independently of eachother hydrogen, C₁-C₅₀alkyl, C₅-C₁₂cycloalkyl, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, C₂-C₅₀alkenyl or C₂-C₅₀alkynyl which can optionally besubstituted one or more times with C₁-C₁₂alkoxy, halogen (especially F),C₅-C₈cycloalkyl, cyano, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or a silyl group;and/or can optionally be further interrupted by one or more —O—, —S—,—NR³⁹—, —CONR³⁹—, —NR³⁹CO—, —COO—, —CO—, or —OCO—; with the proviso thatat least one of the substituents R⁷⁰, R⁷¹ and R⁷² is different fromhydrogen; R³⁸ is C₁-C₅₀alkyl, C₂-C₅₀alkenyl, C₂-C₅₀alkynyl orC₁-C₅₀alkoxy, which can optionally be substituted one or more times withC₁-C₁₂alkoxy, halogen, C₅-C₈cycloalkyl, cyano, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, or a silyl group; and/or can optionally be furtherinterrupted by one or more —O—, —S—, —NR³⁹—, —CONR³⁹—, —NR³⁹CO—, —COO—,—CO—, or —OCO—; and R³⁹ is hydrogen, C₁-C₂₅alkyl, C₁-C₁₈haloalkyl,C₇-C₂₅arylalkyl, or C₁-C₁₈alkanoyl, with the proviso that at least oneof R¹ and R² is a group of formula (II).
 2. The polymer according toclaim 1, wherein —Y(R¹)_(n1)(R²)_(n2)— is a group of formula:

which may optionally be substituted, wherein: R¹ and R² are defined inclaim 1; and R^(1′) and R^(2′) have the meaning of with the proviso thatin case —Y(R¹)_(n1)(R²)_(n2)— is a group of formula:

a and a′ are not
 0. 3. The polymer according to claim 1, wherein Ar¹ andAr^(1′) are independently of each other a group of formula

wherein: R³ and R^(3′) are independently of each other hydrogen,halogen, halogenated C₁-C₂₅alkyl, especially CF₃, cyano, C₁-C₂₅alkyl,especially C₃-C₂₅alkyl, which may optionally be interrupted by one ormore oxygen or sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy; R⁴,R^(4′), R⁵, R^(5′), R⁶ and R^(6′) are independently of each otherhydrogen, halogen, halogenated C₁-C₂₅alkyl, especially CF₃, cyano,C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally be interruptedby one or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, orC₁-C₂₅alkoxy; R⁷, R^(7′), R⁹ and R^(9′) are independently of each otherhydrogen, C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally beinterrupted by one, or more oxygen, or sulphur atoms; orC₇-C₂₅arylalkyl, R⁸ and R^(8′) are independently of each other hydrogen,C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₂₅alkyl, orC₁-C₂₅alkoxy, or C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which mayoptionally be interrupted by one or more oxygen or sulphur atoms; orC₇-C₂₅arylalkyl, R¹¹ and R^(11′) are independently of each otherC₁-C₂₅alkyl group, especially a C₁-C₈alkyl group, C₇-C₂₅arylalkyl, or aphenyl group, which can be substituted one to three times withC₁-C₈alkyl and/or C₁-C₈alkoxy; R¹² and R^(12′) are independently of eachother hydrogen, halogen, cyano, C₁-C₂₅alkyl, especially C₃-C₂₅alkyl,which may optionally be interrupted by one, or more oxygen, or sulphuratoms, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or R¹³; R¹³ is a C₁-C₁₀alkylgroup, or a tri(C₁-C₈alkyl)silyl group; R^(103′) is C₁-C₂₅alkyl,especially C₃-C₂₅alkyl, which may optionally be interrupted by one, ormore oxygen, or sulphur atoms; and R¹¹⁴ and R^(114′) are independentlyof each other hydrogen, cyano, COOR^(103′), a C₁-C₂₅alkyl group, orC₆-C₁₄aryl or C₂-C₂₀heteroaryl.
 4. The polymer according to claim 3,wherein: Ar², Ar^(2′), Ar³ and Ar^(3′) have independently of each otherthe meaning of Ar¹; Ar¹ is defined in claim 3, or are independently ofeach other

R¹⁰⁴ and R^(104′) are independently of each other hydrogen, cyano,COOR¹⁰³, a C₁-C₂₅alkyl group, or C₆-C₁₄aryl or C₂-C₂₀heteroaryl; R¹⁰⁵,R^(105′), R¹⁰⁶ and R^(106′) are independently of each other hydrogen,halogen, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by oneor more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy; R¹⁰⁷is hydrogen, C₇-C₂₅arylalkyl, C₆-C₂₀aryl; C₆-C₂₀aryl which issubstituted by C₁-C₂₅alkyl, or C₁-C₂₅alkoxy; C₁-C₁₈perfluoroalkyl;C₁-C₂₅alkyl; especially C₃-C₂₅alkyl, which may be interrupted by —O—, or—S—; or —COOR¹⁰³; wherein R¹⁰³ is C₁-C₂₅alkyl, especially C₃-C₂₅alkyl,which may optionally be interrupted by one, or more oxygen, or sulphuratoms; R¹⁰⁸ and R¹⁰⁹ are independently of each other hydrogen,C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally be interruptedby one, or more oxygen, or sulphur atoms; or C₇-C₂arylalkyl; R¹¹⁵ andR^(115′) are independently of each other hydrogen, halogen, cyano,C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally be interruptedby one, or more oxygen, or sulphur atoms, C₁-C₂₅alkoxy, C₇-C₂arylalkyl,or

and R¹¹⁶ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group.
 5. Thepolymer according to claim 2, comprising a repeating unit of formula

wherein: R³ and R^(3′) are independently of each other hydrogen,halogen, C₁-C₂₅alkyl, or C₁-C₂₅alkoxy; and R¹, R², R^(1′) and R^(2′) aredefined in claim
 2. 6. The polymer according to claim 1, comprising arepeating unit of formula:

wherein: R³ and R^(3′) are independently of each other hydrogen,fluorine, C₁-C₂₅alkyl, C₁-C₂₅alkoxy; and R¹ and R² are defined inclaim
 1. 7. The polymer according to claim 4, comprising a repeatingunit -[A]-[COM]_(n3)- (V), wherein: A is a unit of formula (I); COM hasthe meaning of Ar²; Ar² is defined in claim 4; n3 is an integer of 1 to4; and COM can be the same or, different in each occurrence.
 8. Thepolymer according to claim 7, wherein the repeating unit-[A]-[COM]_(n3)- is a repeating unit of formula:

wherein: R³ and R^(3′) are independently of each other hydrogen,fluorine, C₁-C₂₅alkyl, or C₁-C₂₅alkoxy; and R¹ and R² are defined inclaim
 1. 9. The polymer according to claim 1, which is a polymer offormula:

wherein: n is 4 to 1000, and R¹ and R² are defined in claim
 1. 10. Thepolymer according to claim 1, wherein: R¹, R², R^(1′) and R^(2′) are agroup of formula:

i is an integer from 1 to 10; and R⁷⁰, R⁷¹ and R⁷² are independently ofeach other hydrogen or C₁-C₅₀alkyl, with the proviso that at least oneof the substituents R⁷⁰, R⁷¹ and R⁷² is different from hydrogen.
 11. Thepolymer according to claim 10, wherein, in the group of formula at leasttwo of the substituents R⁷⁰, R⁷¹ and R⁷² are different from hydrogen.12. The polymer according to claim 10, wherein: R¹, R², R^(1′) andR^(2′) are a group of formula (II):

i is an integer from 1 to 5; and R⁷⁰, R⁷¹ and R⁷² are independently ofeach other hydrogen or C₁-C₃₆alkyl, with the proviso that two of thesubstituents R⁷⁰, R⁷¹ and R⁷² are different from hydrogen.
 13. Anorganic semiconductor material, layer, or component, comprising apolymer according to claim
 1. 14. A semiconductor device, comprising apolymer according to claim
 1. 15. A process for preparing an organicsemiconductor device, the process comprising applying a solution and/ordispersion of a polymer according to claim 1 in at least one organicsolvent to a substrate and removing the at least one solvent.
 16. Adevice, comprising the polymer of claim 1, wherein the device isselected from the group consisting of a photovoltaic device, aphotodiode and an organic field effect transistor.
 17. A compound offormula (X):X³—[Ar³]_(c)—[Ar²]_(b)—[Ar¹]_(a)—Y(R¹)_(n1)(R²)_(n2)—[Ar^(1′)]_(a′)—[Ar^(2′)—[Ar^(3′)]_(c′)—X⁴  (X),wherein: a is 0, 1, 2, or 3; a′ is 0, 1, 2, or 3; b is 0, 1, 2, or 3; b′is 0, 1, 2, or 3; c is 0, 1, 2, or 3; c′ is 0, 1, 2, or 3; n1 is 1, or2; n2 is 1, or 2; Y is a bivalent heterocyclic group, or ring system,which may optionally be substituted; Ar¹, Ar^(1′), Ar², Ar^(2′), Ar³ andAr^(3′) are independently of each other a C₆-C₂₄arylen group, which canoptionally be substituted, or a C₂-C₂₀heteroarylen group, which canoptionally be substituted; R¹ and R² in each occurrence areindependently of each other hydrogen, C₅-C₁₂cycloalkyl, COR³⁸,C₁-C₅₀alkyl, C₃-C₅₀alkenyl, or C₃-C₅₀alkynyl, which can optionally besubstituted one or more times with C₁-C₁₂alkoxy, halogen,C₅-C₈cycloalkyl, cyano, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or a silyl group;and/or can optionally be further interrupted by one or more —O—, —S—,—NR³⁹—, —CONR³⁹—, —NR³⁹CO—, —COO—, —CO—, or —OCO—, or a group offormula:

i is an integer from 1 to 18; R⁷⁰, R⁷¹ and R⁷² are independently of eachother hydrogen, C₁-C₅₀alkyl, C₅-C₁₂cycloalkyl, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, C₂-C₅₀alkenyl or C₂-C₅₀alkynyl which can optionally besubstituted one or more times with C₁-C₁₂alkoxy, halogen (especially F),C₅-C₈cycloalkyl, cyano, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or a silyl group;and/or can optionally be further interrupted by one or more —O—, —S—,—NR³⁹—, —CONR³⁹—, —NR³⁹CO—, —COO—, —CO—, or —OCO—; with the proviso thatat least one of the substituents R⁷⁰, R⁷¹ and R⁷² is different fromhydrogen; R³⁸ is C₁-C₅₀alkyl, C₂-C₅₀alkenyl, C₂-C₅₀alkynyl orC₁-C₅₀alkoxy, which can optionally be substituted one or more times withC₁-C₁₂alkoxy, halogen, C₅-C₈cycloalkyl, cyano, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, or a silyl group; and/or can optionally be furtherinterrupted by one or more —O—, —S—, —NR³⁹—, —CONR³⁹—, —NR³⁹CO—, —COO—,—CO—, or —OCO—; and R³⁹ is hydrogen, C₁-C₂₅alkyl, C₁-C₁₈haloalkyl,C₇-C₂₅arylalkyl, or C₁-C₁₈alkanoyl; X³ and X⁴ are independently of eachother hydrogen, halogen, ZnX¹², —SnR²⁰⁷R²⁰⁸R²⁰⁹; R²⁰⁷, R²⁰⁸ and R²⁰⁹ areidentical or different and are H or C₁-C₆alkyl, wherein two radicalsoptionally form a common ring and these radicals are optionally branchedor unbranched and X¹² is a halogen atom; or —OS(O)₂CF₃, —OS(O)₂-aryl,—OS(O)₂CH₃, —B(OH)₂, —B(OY¹)₂,

—BF₄Na, or —BF₄K; Y¹ is independently in each occurrence a C₁-C₁₀alkylgroup; Y² is independently in each occurrence an optionally substitutedC₂-C₁₀alkylene group; and Y¹³ and Y¹⁴ are independently of each otherhydrogen, or a C₁-C₁₀alkyl group.